CN113134384A - Method for reducing emission of nitrogen oxides in iron ore sintering process - Google Patents
Method for reducing emission of nitrogen oxides in iron ore sintering process Download PDFInfo
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- CN113134384A CN113134384A CN202010067687.6A CN202010067687A CN113134384A CN 113134384 A CN113134384 A CN 113134384A CN 202010067687 A CN202010067687 A CN 202010067687A CN 113134384 A CN113134384 A CN 113134384A
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- sintering
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- iron ore
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- 238000005245 sintering Methods 0.000 title claims abstract description 92
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 36
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 36
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000005342 ion exchange Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002808 molecular sieve Substances 0.000 claims abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 230000007480 spreading Effects 0.000 abstract description 3
- 238000003892 spreading Methods 0.000 abstract description 3
- 239000003546 flue gas Substances 0.000 description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 21
- 230000009467 reduction Effects 0.000 description 18
- 239000000446 fuel Substances 0.000 description 9
- 239000002912 waste gas Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000009818 secondary granulation Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 4
- 239000003830 anthracite Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
Abstract
The invention discloses a method for reducing nitrogen oxide emission in an iron ore sintering process, which comprises the following steps: (1) taking molecular sieve NaZSM-5 with Si/Al of 25-200 and copper acetate solution to perform an ion exchange method according to the mass ratio to prepare a Cu-ZSM-5 catalyst; (2) adding the mixture to a sinter mix
Description
Technical Field
The invention belongs to the technical field of environmental protection and waste gas treatment, and particularly relates to a method for reducing nitrogen oxide emission in an iron ore sintering process.
Background
NOxIs a well-known atmospheric pollutant which seriously affects the survival and development of human beings. Air pollutant NOxMainly refers to NO generated in the coal combustion process and a small amount of NO2And also includes trace amount of N2O、N2O3And the like. NOxThe direct and indirect hazards to humans themselves and the environment have far outweighed other pollutants. While the sintering process in the iron and steel industry is accompanied by the combustion of fuel, a large amount of nitrogen oxides can be discharged, and the discharge amount of the nitrogen oxides can account for NO in the iron and steel industryxMore than 50% of the total discharge.
NO reduction by adding metal additives to the sintering raw materialxThe emission is one of the research hotspots in the aspect of denitration at home and abroad at present; furthermore, there are studies showing that the addition of certain amounts of calcium-containing compounds to the sinter may reduce NOxAnd (4) discharging the amount.
Yanguang Chen et al have invented reduction of sintering NO by coke powder modificationxDischarging of loaded K in coke breeze2O3CaO and CeO2Can reduce fuel nitrogen to NO during coke combustionx(ISIJ International, 2004, 44(3): 470-475).
Chin-Lu MO et al found that adding hydrocarbons into the sinter can significantly reduce NO, and the blending of hydrocarbons such as wheat straw, lignin and saccharides enhances the air permeability of the sinter bed and reduces the high-temperature duration of the combustion zone; adding 1% of sugar, NOxThe content is reduced from 223ppm to 160 ppm; the productivity was from 37.5 t/(m)224h) to 45.4 t/(m)224 h); the drum index of the sintered ore is kept unchanged, and the low-temperature reduction degradation rate is reduced from 31.5% to 27.3% (ISIJ International, 1997, 37 (4): 350-.
Denitration technology for sintering process is to reduce NO by controlling operating conditions or adding certain additives in the sintering processxA method of (1). Due to NO in sintering flue gasxThe concentration is low, the flue gas flow is large, the dust amount is large, and the traditional flue gas denitration method is difficult to apply to the sintering process. Effective NO inhibition during sintering is therefore soughtxThe released additive has great significance for the development of the future steel industry.
Disclosure of Invention
The invention aims to solve the technical problem of high emission of nitrogen oxides in the steel sintering process in the prior art, and provides a method for reducing the emission of the nitrogen oxides in the sintering process, so that the emission standard is reached, and the load of a tail-end SCR denitration device is reduced.
The technical problem to be solved can be implemented by the following technical scheme.
A method for reducing the emission of nitrogen oxides in the process of sintering iron ores is characterized by comprising the following steps:
(1) taking molecular sieve NaZSM-5 with Si/Al of 25-200 and copper acetate solution to perform an ion exchange method according to the mass ratio to prepare a Cu-ZSM-5 catalyst;
(2) adding the mixture to a sinter mix
Uniformly mixing the Cu-ZSM-5 catalyst in a mass ratio; or uniformly spreading the catalyst with the above addition amount on the bottom layer of the sintering material, and then sintering.
As a further improvement of the technical scheme, in the step (1) preparation, NaZSM-5 is placed in a copper acetate solution, ion exchange is carried out in a water bath kettle, suction filtration is carried out, filter cakes are washed by deionized water until the filtrate does not contain copper ions, air blowing drying is carried out, roasting is carried out in a muffle furnace, and secondary exchange is carried out, so that the Cu-ZSM-5 catalyst is obtained.
Further, NaZSM-5 is placed in 0.01mol/L copper acetate solution, ion exchange is carried out for 8 hours in a water bath kettle at the temperature of 40 ℃, suction filtration is carried out, filter cakes are washed by deionized water until the filtrate does not contain copper ions, then forced air drying is carried out for 8 hours at the temperature of 120 ℃, roasting is carried out for 3 hours in a muffle furnace at the temperature of 500 ℃, and then secondary exchange is carried out, so that the Cu-ZSM-5 catalyst is obtained.
Also as a further improvement of the present solution, said Si/Al is 25, 40, 100 or 200.
Also as a further improvement of the technical proposal, the molecular sieve NaZSM-5 is a mixture of one or more of Si/Al selected from 25, 40, 100 and 200.
The method for reducing the emission of nitrogen oxides in the sintering process of the iron ore by adopting the technical scheme has the following beneficial effects:
the method can effectively reduce the discharge amount of nitrogen oxides in the sintering process, belongs to a clean production technology, has small investment and simple operation, and does not change the prior sintering process flow. By adopting the technical scheme provided by the invention, the load of the tail-end sintering flue gas denitration device can be effectively reduced, and the emission of nitrogen oxides can meet the requirements of national emission standards.
Detailed Description
In order to reduce the emission of nitrogen oxides in the steel sintering process, the invention provides a method for reducing the emission of nitrogen oxides in the sintering process by adding an effective catalyst, which comprises the selection and preparation of a high-efficiency catalyst and sintering after adding the catalyst in a sintering mixture.
The method is realized by the following technical scheme:
the catalyst is prepared by an ion exchange method of molecular sieve NaZSM-5(Si/Al is 25-200) and a copper acetate solution. Placing NaZSM-5 in a copper acetate solution, performing ion exchange in a water bath, performing suction filtration, washing a filter cake with deionized water until the filtrate does not contain copper ions, performing forced air drying, roasting in a muffle furnace, and performing secondary exchange to obtain a Cu-ZSM-5 catalyst;
② adding into the sintering mixture
The catalyst is evenly mixed or evenly spread on the bottom layer of the sintering material, and then sintering is carried out.
The Cu-ZSM-5 catalyst can efficiently reduce the discharge amount of nitrogen oxides in the sintering process, and the usage amount of the catalyst is very small, so that the process is economic; the catalyst is used for in-situ emission reduction of NOx in the sintering process, is a Cu-ZSM-5 catalyst prepared by carrying out an ion exchange method on a molecular sieve NaZSM-5 and a copper acetate solution, and has high denitrification activity. The Cu-ZSM-5 catalyst is added in the process of mixing the sintering material and can also be paved on the bottom layer of the sintering material, the operation process is simple, and the industrial sintering process flow is not changed.
The invention is further illustrated by the following more specific examples.
Example 1:
preparing iron ore sintering mixture, wherein the fuel anthracite accounts for 5%, and granulating. Taking 250g of the sintering mixture, adding NaZSM-5 (mass ratio Si/Al is 25) and a copper acetate solution in the secondary granulation process to perform primary ion exchange to obtain a Cu-ZSM-5 catalyst, uniformly mixing the Cu-ZSM-5 catalyst and the sintering mixture according to the mass ratio
And finally, filling the mixture into a sintering cup for micro-sintering experiment. In the whole sintering process, NO in sintering waste gas is recorded on line through a flue gas analyzerxThe final NO reduction amount in the flue gas is 12.4 percent, and the NO content in the flue gas is reduced2The displacement reduction was 25.1%.
Example 2:
preparing iron ore sintering mixture, wherein fuel coke accounts for 5%, and granulating. Taking 250g of the sintering mixture, adding NaZSM-5 (mass ratio Si/Al is 100) and a copper acetate solution in the secondary granulation process to perform primary ion exchange to obtain a Cu-ZSM-5 catalyst, uniformly mixing the Cu-ZSM-5 catalyst and the sintering mixture according to the mass ratio
And finally, filling the mixture into a sintering cup for micro-sintering experiment. In the whole sintering process, NO in sintering waste gas is recorded on line through a flue gas analyzerxThe final NO reduction amount in the flue gas is 21.56 percent, and the NO content in the flue gas is reduced2The displacement reduction was 63.2%.
Example 3:
preparing iron ore sintering mixture, wherein the fuel anthracite accounts for 5%, and granulating. Taking 250g of the sintering mixture, adding NaZSM-5 (mass ratio Si/Al is 200) and a copper acetate solution in the secondary granulation process to perform primary ion exchange to obtain a Cu-ZSM-5 catalyst, uniformly mixing the Cu-ZSM-5 catalyst and the sintering mixture according to the mass ratio
And finally, filling the mixture into a sintering cup for micro-sintering experiment. In the whole sintering process, NO in sintering waste gas is recorded on line through a flue gas analyzerxThe reduction of NO in the final smoke is 35.6 percent, and the reduction of NO2 is 72.6 percent.
Example 4:
preparing iron ore sintering mixture, wherein the fuel anthracite accounts for 5%, and granulating. Taking 250g of the sintering mixture, adding NaZSM-5 (mass ratio Si/Al is 25) and a copper acetate solution in the secondary granulation process to perform secondary ion exchange to obtain a Cu-ZSM-5 catalyst, uniformly mixing the Cu-ZSM-5 catalyst and the sintering mixture according to the mass ratio
And finally, filling the mixture into a sintering cup for micro-sintering experiment. In the whole sintering process, NO in sintering waste gas is recorded on line through a flue gas analyzerxThe final NO reduction amount in the flue gas is 30.4 percent, and the NO content in the flue gas is reduced2The displacement reduction was 65.1%.
Example 5:
preparing iron ore sintering mixture, wherein fuel coke accounts for 5%, and granulating. Taking 250g of the sintering mixture, spreading NaZSM-5 (mass ratio Si/Al is 25) and a copper acetate solution in the bottom layer of a sintering cup, carrying out primary ion exchange to obtain a Cu-ZSM-5 catalyst, uniformly mixing, adding 4 per mill of the sintering material according to the mass ratio, and finally loading the sintering material into a micro-sintering experiment. In the whole sintering process, NO in sintering waste gas is recorded on line through a flue gas analyzerxThe final NO reduction amount in the flue gas is 58.1 percent, and the NO content in the flue gas is reduced2The displacement reduction was 89.1%.
Example 6:
preparing iron ore sintering mixture, wherein the fuel anthracite accounts for 5%, and granulating. Taking 250g of the sintering mixture, adding NaZSM-5 (mass ratio Si/Al is 40) and a copper acetate solution in the secondary granulation process to perform primary ion exchange to obtain a Cu-ZSM-5 catalyst, uniformly mixing the Cu-ZSM-5 catalyst and the sintering mixture according to the mass ratio
And finally, filling the mixture into a sintering cup for micro-sintering experiment. In the whole sintering process, NO in sintering waste gas is recorded on line through a flue gas analyzerxThe final NO reduction amount in the flue gas is 32.4 percent, and the NO content in the flue gas is reduced2The displacement reduction was 75.3%.
Example 7:
preparing iron ore sintering mixture, wherein fuel coke accounts for 5%, and granulating. Taking 250g of the sintering mixture, adding NaZSM-5 (mass ratio Si/Al is 25) and a copper acetate solution in the secondary granulation process to perform secondary ion exchange to obtain a Cu-ZSM-5 catalyst, uniformly mixing the Cu-ZSM-5 catalyst and the sintering mixture according to the mass ratio
And finally, filling the mixture into a sintering cup for micro-sintering experiment. In the whole sintering process, NO in sintering waste gas is recorded on line through a flue gas analyzerxThe final NO reduction in the flue gas is 19.4%, NO2The displacement reduction was 35.1%.
Claims (5)
1. A method for reducing nitrogen oxide emission in the process of sintering iron ore is characterized by comprising the following steps:
(1) taking molecular sieve NaZSM-5 with Si/Al of 25-200 and copper acetate solution to perform an ion exchange method according to the mass ratio to prepare a Cu-ZSM-5 catalyst;
(2) adding the mixture to a sinter mix
Uniformly mixing the Cu-ZSM-5 catalyst in a mass ratio; or uniformly paving the catalyst in the above addition amount on the bottom layer of the sintering material, and then sintering.
2. The method for reducing the emission of nitrogen oxides during the sintering of iron ore according to claim 1, wherein in the step (1), NaZSM-5 is placed in a copper acetate solution, ion exchange is carried out in a water bath, suction filtration is carried out, deionized water is used for washing a filter cake until the filtrate does not contain copper ions, air-blast drying is carried out, roasting is carried out in a muffle furnace, and secondary exchange is carried out to obtain the Cu-ZSM-5 catalyst.
3. The method for reducing the emission of nitrogen oxides during the sintering of iron ore according to claim 2, characterized in that NaZSM-5 is placed in 0.01mol/L copper acetate solution, ion exchange is carried out for 8h in a water bath kettle at 40 ℃, suction filtration is carried out, filter cake is washed by deionized water until the filtrate does not contain copper ions any more, then air-blast drying is carried out for 8h at 120 ℃, then roasting is carried out for 3h at 500 ℃ in a muffle furnace, and then secondary exchange is carried out, thus obtaining the Cu-ZSM-5 catalyst.
4. The method of reducing nitrogen oxide emissions from iron ore sintering according to claim 1, wherein the Si/Al is 25, 40, 100 or 200.
5. The method of reducing nitrogen oxide emissions from iron ore sintering process according to claim 1, wherein the molecular sieve NaZSM-5 is a mixture of one or more Si/Al selected from 25, 40, 100 and 200.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010067687.6A CN113134384A (en) | 2020-01-20 | 2020-01-20 | Method for reducing emission of nitrogen oxides in iron ore sintering process |
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| CN202010067687.6A CN113134384A (en) | 2020-01-20 | 2020-01-20 | Method for reducing emission of nitrogen oxides in iron ore sintering process |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4054640A (en) * | 1975-05-16 | 1977-10-18 | Nippon Kokan Kabushiki Kaisha | Method of removing nitrogen oxides from an exhaust |
| CN101259368A (en) * | 2008-04-11 | 2008-09-10 | 浙江工业大学 | Method for catalytic oxidation NO with ZSM-5 type molecular sieve as catalyst |
-
2020
- 2020-01-20 CN CN202010067687.6A patent/CN113134384A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4054640A (en) * | 1975-05-16 | 1977-10-18 | Nippon Kokan Kabushiki Kaisha | Method of removing nitrogen oxides from an exhaust |
| CN101259368A (en) * | 2008-04-11 | 2008-09-10 | 浙江工业大学 | Method for catalytic oxidation NO with ZSM-5 type molecular sieve as catalyst |
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Application publication date: 20210720 |